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United States Patent |
5,166,002
|
Shepard
,   et al.
|
November 24, 1992
|
High-temperature, high-emissivity, optically black boron surface
Abstract
An article of manufacture comprises a substrate and an optically black
surface on the substrate and having an absorptivity of more than about
0.89 and an emissivity more than about 0.86. The surface comprises boron
particles plasma spray applied to the substrate using a powder selected
from the group consisting of crystalline boron having a particle size
finer than about 200 mesh and amorphous boron.
Inventors:
|
Shepard; Donald F. (Evergreen, CO);
Fenolia; Robert J. (Broomfield, CO);
Nagle; Dennis C. (Ellicott City, MD);
Marousek; Michael E. (Baltimore, MD)
|
Assignee:
|
Martin Marietta Corporation (Denver, CO)
|
Appl. No.:
|
699884 |
Filed:
|
June 27, 1991 |
Current U.S. Class: |
428/457; 427/162; 427/376.1; 427/419.3; 427/446; 427/453; 428/689; 428/704 |
Intern'l Class: |
B32B 015/04 |
Field of Search: |
427/423,34,162,228,376.1,419.3
428/457,689,704
|
References Cited
U.S. Patent Documents
3231416 | Jan., 1966 | Fuller | 427/34.
|
3231417 | Jan., 1966 | Fuller | 427/423.
|
4342734 | Aug., 1982 | Kumar et al. | 427/34.
|
5035949 | Jul., 1991 | Shepard et al. | 427/34.
|
Primary Examiner: Lusignan; Michael
Assistant Examiner: Dudash; Diana L.
Attorney, Agent or Firm: Tarolli, Sundheim & Covell
Goverment Interests
This invention was made with Government support under Contract
F33615-81-C-5117 awarded by the Department of the Air Force. The
government has certain rights in this invention.
Parent Case Text
This is a divisional of co-pending Application Ser. No. 07/280,146, filed
on Dec. 5, 1988, now U.S. Pat. No. 5,035,949, issued Jul. 30, 1991, and
application Ser. No. 07/704,129, filed May 22, 1991.
Claims
Having described a preferred embodiment of the invention, I claim:
1. A method for the preparation of an optically black article of
manufacture comprising the steps of:
plasma spray applying onto a substrate a boron powder of at least about 90%
purity selected from the group consisting of crystalline boron having a
particle size of about -200 mesh and amorphous boron,
said plasma spraying being under conditions effective to obtain a boron
coating bonded to said substrate having an irregular surface morphology of
peaks and valleys,
said coating having an absorptivity of more than about 0.89 and an
emissivity of more than about 0.86.
2. The method of claim 1 wherein said substrate is selected from the group
consisting of titanium, nickel, molybdenum and alloys thereof.
3. The method of claim 1 wherein said boron powder is -325 mesh and blended
with ceramic oxide microspheres.
4. An optically black sunshade prepared by the method of claim 1.
5. A method for the preparation of an optically black article of
manufacture comprising the steps of:
plasma spray applying onto a substrate a boron powder of at least about 90%
purity selected from the group consisting of crystalline boron having a
particle size of about -200 mesh and amorphous boron,
calcining the plasma-spray-applied boron surface,
said surface having an absorptivity of more than about 0.89 and an
emissivity of more than about 0.86.
6. A method for plasma spraying boron onto a substrate selected from the
group consisting of molybdenum, tantalum, niobium, tungsten, and copper
for the preparation of an optically black article of manufacture,
comprising the steps of:
providing said substrate;
plasma spray applying a bond coat which is a mixture of molybdenum and
titanium onto said substrate;
plasma spray applying onto said bond coat a boron powder of at least about
90% purity selected from the group consisting of crystalline boron having
a particle size of about -200 mesh and amorphous boron;
said plasma spraying of said boron powder being under conditions effective
to obtain a boron coating having an irregular surface morphology of peaks
and valleys;
said article having an absorptivity of more than about 0.89 and an
emissivity of more than about 0.86.
7. The method of claim 6 wherein said substrate has a thickness less than
about 0.030 inches.
8. The method of claim 7 wherein said bond coat is applied without
externally applied substrated heating.
9. The method of claim 6 wherein said bond coat is an 80/20 blend, on a
weight basis, of molybdenum and titanium.
10. The method of claim 6 further including the step of calcining the
plasma-spray-applied boron surface.
11. The method of claim 6 wherein said boron powder is -325 mesh and
blended with ceramic oxide microspheres.
Description
The present invention relates to optically black boron surface which are
applied by plasma-jet spray onto a substrate. For purposes of the present
application, the term "optically black" means capable of energy absorption
in both the visible (solar) region and the infrared region. In such
spectral regions, the surfaces of the present invention have both a high
absorptivity of solar radiation and a high emissivity in the infrared
region. The surfaces of the present invention also have a high thermal
stability, are suitable for use in nuclear environments, and are
substantially inert to many chemical and oxidizing environments.
BACKGROUND OF THE PRESENT INVENTION
Prior U.S. Pat. No. 4,342,734, issued Aug. 3, 1982 to Dumar and Das,
discloses the preparation of thick, dense wafers of crystalline
gamma-tetragonal boron by plasma-jet applying beta-rhombohedral boron in
powder form onto a substrate and rapidly cooling the molten particles. The
beta-boron powder had a particle size of -100 mesh. The patent makes no
mention of the optical properties of the cooled deposit nor reference to
the formation of optically black surfaces. The patent is also silent on
other properties such as resistance to high temperature degradation or
corrosion resistance to chemical or oxidizing environments.
Prior U.S. Pat. No. 3,231,416, issued Jan. 25, 1966, to Fuller, discloses
the preparation of zirconia-boron ablation coatings by plasma-jet
spraying. An example of a powder used in the '416 patent contained 60
volume percent zirconia (325 mesh) and 40 volume percent boron (100 mesh).
The coatings were said to be capable of withstanding temperatures of about
2280.degree. C. during a ten second test period. This, in part, was
attributed to good thermal emittance or ability to radiate heat away from
the coated body. As in the '734 patent, no reference is made to the
infrared or visible wavelength absorption or other properties which
characterize the present invention.
Also of interest are prior U.S. Pat. Nos. 4,503,085, dated Mar. 5, 1985,
issued to Dickson et al.; 4,526,618, issued Jul. 2, 1985, to Keshavan et
al.; and 4,696,855, dated Sep. 29, 1987, issued to Pettit, Jr., et al.
BRIEF SUMMARY OF THE INVENTION
The present invention resides broadly in an article or manufacture
comprising a substrate and an optically black surface on said substrate
having an absorptivity of more than about 0.89 and an emissivity more than
about 0.86, said surface comprising boron particles plasma spray applied
to said substrate using a boron powder selected from the group consisting
of crystalline boron having a particle size finer than about 200 mesh and
amorphous boron.
Preferably, the crystalline boron has a powder size finer than about 325
mesh.
It is also preferable that the boron powder have a purity of at least about
95%.
Applications for the articles of manufacture of the present invention
include sunshades, surfaces exposed to high temperature environments such
as laser beams, thermal control surfaces such as high temperature
radiators for nuclear reactors or neutron absorbers, and surfaces exposed
to corrosive chemicals or oxidative agents such as linings for chemical
tanks, flow lines and nitrogen tetroxide containing propellant tanks. By
the term "sunshade", it is meant any baffle or surface positioned for the
control of light in such applications as telescopes, laser beam control,
energy absorbers or radiators, and spacecraft optical systems.
Preferred substrated in accordance with the present invention are titanium,
nickel, molybdenum, and alloys thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention and advantages thereof will become more apparent upon
consideration of the following specification, with reference to the
accompanying drawings, in which:
FIG. 1 is a surface view of an optically black boron surface prepared by
plasma spray application of a crystalline boron powder onto a substrate.
The photograph of FIG. 1 was taken at 250 K magnification using an
electron microscope; and
FIG. 2 is photograph of a portion of the surface of FIG. 1 taken at 1,000 X
magnification using an electron microscope; and
FIG. 3 is a surface view of an optically black boron surface prepared by
plasma spray application of amorphous boron onto a substrate. The
photograph of FIG. 3 was taken at 250 magnification using an electron
microscope.
DETAILED DESCRIPTION OF THE INVENTION AND BEST MODE
The plasma spray process is well known and fully described in numerous
prior patents, including, by way of example, prior U.S. Pat. No. 4,526,618
referred to above. The disclosure of the '618 patent in this respect is
incorporated by reference herein.
In the plasma spray process, a gas is used as a heating and carrier medium.
A preferred gas is an inert gas such as argon. A stream of the gas is
heated to a high temperature by being passed between electric arc-forming
electrodes. The plasma expands due to its high heat and kinetic energy and
produces a high velocity directional jet. Boron particles are injected
into the rapidly flowing heated stream wherein they are heated to a
sufficiently high temperature to become melted or softened. The plasma jet
is directed at a target surface, depositing the molten or softened boron
particles onto the surface. The boron particles are allowed to cool by
exposure to ambient conditions, aided by the application of cooling water
to the backside of the substrate. This allows the boron particles to
become bonded to the surface and to each other in the formation of a thin
layer.
For purposes of the present application, the term "plasma spray process"
includes derivatives of the process capable of heating the boron particles
to a high enough temperature to soften or melt the particles, such as
detonation gun spraying.
Practically any substrate, including most metals, and even plastics, which
are capable of withstanding the high temperature gas stream, and adapted
to receive the molten or softened metal particles, can be employed. Boron
has a coefficient of thermal expansion of about 4.6.times.10.sup.-6
in./in./.degree.F., and titanium has a coefficient of expansion very close
to that, about 4.7.times.10.sup.-6 in./in./.degree.F., making titanium or
a titanium alloy a preferred substrate. However, the present invention has
been successfully practiced with other substrate surfaces, such as
molybdenum and nickel.
It is well known that certain substrates such as molybdenum, tantalum,
niobium, tungsten and copper are difficult to coat by plasma spray and
obtain a good bond. To further compound the problem, aeronautical and
space uses for the present invention require that the substrates by
relatively thin (e.g., less than 0.030 inches) and thus lightweight. This
thinness of the substrates makes it impractical to subject them to severe
surface preparation such as abrasion and or substrate heating. In an
aspect of the present invention, ti was found that these disadvantages
could be overcome by applying, by plasma spray, a molybdenum titanium
self-bonding coat, preferably a mixture of 80% molybdenum/20% titanium, to
which a boron top coat would adhere.
The bond coat could be applied without heating the substrate, adhered well
to such substrates as molybdenum and provided an excellent surface for
application of a top coat such as boron.
The boron powder employed in the practice of the present invention can be
either a crystalline boron or amorphous boron. Both have been successfully
plasma sprayed onto a substrate. Preferably, the boron has a purity of at
least about 90%, more preferably, at least about 95%. The boron has to be
in fine powder form, for instance, that of amorphous boron which typically
has an average particle size less than about 10 microns. In the case of
the crystalline boron, this should have an average particle size finer
than about 200 mesh, preferably an average particle size finer than about
325 mesh.
The fine particle sized boron tended to be hygroscopic and tended to pack.
This problem was overcome by either forming the boron into aggregates
using an organic binder and mechanically grinding and sieving the
aggregates to a flowable particle size such as -325 mesh, or by adding a
small amount of a flow enhancer such as a ceramic oxide to the boron
powder to increase its flowability. One suitable binder employed was
polyvinyl alcohol, added as a 2% by weight aqueous solution to the powder,
which was then dried and subjected to grinding and sieving to -325 mesh.
The amount of binder used was about five weight percent based on the
weight of the boron. Numerous fine particle size ceramic oxide powders are
commercially available. One that was successfully employed was a silica
ceramic in the form of microspheres marketed by 3M under the trademark
"Glass Bubbles A38/4000". The amount used was about 10-70 weight percent,
based on the weight of the entire composition. These "Glass Bubbles" had a
particle size such that a maximum of 5% by weight was retained on a U.S.
No. 80 standard sieve. Yttria stabilized zirconium oxide in the amount up
to about 70 volume percent (basis entire composition) has also been
successfully employed as a ceramic oxide flow enhancing agent. An example
of another ceramic oxide is aluminum oxide.
The boron surfaces which are applied to a substrate by the plasma jet
process have an irregular surface morphology of peaks and valleys which
gives, without further treatment, good absorptivity and emissivity making
such surfaces useful as optical baffles. However, it was found that the
absorptivity and emissivity could be further increased by subjecting the
surfaces to calcination. This was carried out at an elevated temperature,
for instance about 400.degree. C. to about 600.degree. C. for 30 to 60
minutes in an air atmosphere. By calcination, the absorptivity can be
increased up to about 0.95, and the emissivity similarly may be increased,
for instance up to about 0.93.
The coating depths were determined to be about 200.+-.15 microns.
The following examples illustrate the practice of the present invention. In
these examples, absorptivity and emissivity were measured using a
Gier-Dunkle MF-251 solar reflectrometer and a Gier-Dunkle DB-100 infrared
reflectometer.
EXAMPLE 1
This Example illustrates the preparation of an optically black sunshade by
application of crystalline boron to a substrate. The substrate selected in
this Example was a titanium, aluminum, vanadium alloy having six parts
aluminum and four parts vanadium to 100 parts titanium (Ti-6Al-4V).
The surface of the substrate was prepared by degreasing it with
1,1,1-trichloroethane. Application of the boron was carried out using a
plasma spray gun manufactured by the Metco Division of Perkin-Elmer,
Westbury, New York, Model No. 7M.
The boron was crystalline boron marketed by Consolidated Astronautics
identified as having a purity of 96.6% and a particle size of -325 mesh.
Analysis of the powder revealed that it had an average particle size of
about 20 microns with 90% of the particles being less than about 90
microns. To improve the flowability of the boron powder into the plasma
spray gun, the powder was formed into small aggregates by mixing the
powder with 1-2% by weight (based on the weight of boron) of a 2% by
weight solution of polyvinyl alcohol, which mixture was then dried. The
dried aggregates were mechanically ground and sieved to -325 mesh (U.S.
Sieve).
The spray settings on the plasma spray gun were:
______________________________________
Primary Gas Secondary Gas
Parameter Argon Hydrogen
______________________________________
Pressure 100 psi 50 psi
Flow 80 (setting)
15-20 (setting)
Nozzle -- Gh
Current -- 500 Amps
Voltage -- 65 V
Power -- 32.5 KW
______________________________________
Powder Feeder-4MP-dual
______________________________________
Powder Port No. 2 at about 90
Powder port shaft A
Carrier gas flow 37
Air vibrator 15-20 psi
Powder feed rate indicator
80 (setting)
______________________________________
The spraying was carried out using a gun-to-work distance of about 10-15
centimeters. A thin film was desired, just covering the substrate, so that
the application was by hand making four fast passes with the gun. The
coated substrate was cooled by application of water to the backside of the
substrate. The absorptivity of the boron surface was about 0.93 and the
emissivity was about 0.87. The coating had a dark grey appearance and was
considered to be suitable, without further treatment, for use as an
optically black sunshade.
It was found that the optical properties of the surface could be somewhat
further increased by exposure of the boron surface to calcination. In this
Example, calcination was carried out at 500.degree. C. to 600.degree. C.
for about two hours, in air, and resulted in an increase in absorptivity
to about 0.95 (about a 30% increase), but no increase in emissivity.
Following calcination, the coating had a black appearance.
EXAMPLE 2
This Example illustrates the preparation of an optically black sunshade
using an amorphous boron. The boron was marketed by Consolidated
Astronautics and was identified as having a purity of about 96% and an
average particle size of about five microns. The average particle size was
determined to be slightly less than five microns.
To increase the flowability of the amorphous boron, the boron was mixed
with 32% by weight, based on the weight of the total composition, of fine
particle size glass ceramic microspheres marketed by 3M under the trade
designation "Glass Bubbles A38/4000". The microspheres had a particle size
such that a maximum of 5% by weight was retained on a U.S. No. 80 standard
sieve.
The spray conditions and equipment used were the same as in Example 1
except that the gun to work distance employed was about 5-10 centimeters.
Also the substrate employed was nickel (Ni-201) instead of the titanium
alloy of Example 1, and the substrate was prepared, prior to plasma
spraying the amorphous boron, by application of a standard nickel bond
coat consisting of a nickel, chromium, aluminum alloy marketed by Metco
under the trade designation "Metco 443". The bond coat was plasma spray
applied to the Nickel substrate using essentially the same spray
conditions as in Example 1, giving a thin layer of about 0.002-0.005
inches.
Following spraying, the samples were subjected to calcination under an air
atmosphere for about two hours at 600.degree. C. Calcination gave a
surface having a visually black appearance and increased the absorptivity
from about 0.90 to about 0.93. The emissivity following calcination was
about 0.90. The surface had a visually black appearance.
Samples of optically black baffles prepared in accordance with this Example
were subjected to a continuous wave laser test at 10.6 microns. There was
no damage to the boron surface that could be determined by visual
inspection. Absorptivity decreased slightly from about 0.93 to about 0.92.
Emissivity decreased slightly from about 0.90 to about 0.89.
EXAMPLE 3
Similar samples as in Example 2 were prepared using molybdenum as the
substrate.
It is well known that materials such as molybdenum, tantalum, niobium,
tungsten and copper are difficult materials on which to deposit
self-bonding surface coatings by plasma spray. In the present instance,
the uses of principle intersect are space or aeronautical associated,
where light weight is desired. Accordingly the substrate in this example
had a thickness of only about 0.015 inches. This prevented the surface
from being intensively prepared, for instance by surface roughening, or
heated to an elevated temperature prior to applying a plasma sprayed boron
coat.
It was found that these difficulties could be overcome by applying a
molybdenum/titanium bond coat to the substrate prior to application of the
boron top coat. Only through cleaning of the substrate was required, and
no mechanical roughening of the surface such as by rough grit blasting was
necessary. The bond coat adhered well and provided a surface roughness
ideally suited for the reception of sprayed top coats.
In this example, the bond coat was an 80/20 blend of molybdenum and
titanium. The substrate was cleaned using 1,1,1-trichloroethane and a
light sand blast. The conditions of application and spray gun were:
______________________________________
Spray Gun
______________________________________
Type - 7MB (Metco)
Nozzle - GH
Uni-jet Ring
Argon Insulator
#2 Powder Port at 90
______________________________________
Gas Pressure Gas Flow
______________________________________
Primary (argon) - 100 psi
Primary (argon) - 80 psi
Secondary (hydrogen) - 5 psi
Secondary (hydrogen) - 15 psi
______________________________________
Power Powder Feed
______________________________________
Unit Model - 7MR (Metco)
Unit - 4MP Dual
Arc Amps - 500 Powder Port Shaft - A
Arc Volts - 60-65
Carrier Gas Pressure - 100 psi
Flow Meter Reading - 47 psi
Feed Rate Indicator - 100-125
Air Vibrator Pressure - 20-25
psi
______________________________________
The thickness of the bond coat was about 0.002-0.005 inches.
It should be noted that this bond coat can be successfully applied to
almost any metal, and was successfully applied to such substrates as
nickel, titanium and the titanium-aluminum vanadium alloy of Example 1, in
addition to molybdenum, giving in each instance excellent bond strength
and the advantages noted above with regard to application to a molybdenum
substrate.
In this Example, the same spray conditions and amorphous boron as employed
in Example 2 were used. The amorphous boron surface when plasma sprayed
onto the bond coat gave an absorptivity of about 0.97 and emissivity of
about 0.88. These samples also were deemed to be within the scope of the
present invention. No posttreatment such as calcination was used.
These samples were exposed to the same continuous wave laser test as in
Example 2, and the samples also passed visual examination. The
absorptivity was found to decrease slightly to about 0.93, whereas the
emissivity remained generally constant.
The sample of Example 3 was the subject of the photograph of FIG. 3, taken
at 100X magnification. As shown in this Figure, the boron particles
formed, on impact, a rough, nodular, layered surface with deep
indentations capable of trapping light.
EXAMPLE 4
In this Example, the same crystalline boron as in Example 1 was plasma
spray applied to a nickel (Ni-201) substrate (precoated with a nickel,
chromium, aluminum alloy bond coat, Metco 443, as in Example 2),
subsequently calcined, and then exposed to the same continuous wave laser
test as in Examples 2 and 3. To increase the flowability of the
crystalline boron, the boron was mixed with 32% by weight of glass ceramic
microspheres as in Example 2. The procedures of plasma spray application
and calcination were the same as in Example 1. Following plasma spray
application and following calcination, the solar absorptivity was
determined to be about 0.92 and about 0.97, respectively. The emissivity
after plasma spray application and after calcination remained constant at
about 0.88. Following the continuous wave laser test, absorptivity dropped
slightly to about 0.93 and emissivity decreased slightly to about 0.87.
These samples were deemed also to be within the scope of the present
invention, and were deemed to have passed the laser test, both with regard
to measured absorptivity and emissivity, and by visual examination.
The physical characteristics of the surfaces of this Example are shown in
FIGS. 1 and 2, taken at 250X and 1,000X magnification, respectively. As
shown in these Figures, the boron particles formed on impact, a rough,
platelet layered surface with deep indentations capable of trapping light.
In the surfaces of both Examples 3 and 4, the nodules or platelets provided
a large number of points of absorption separated from each other by a
spectrum of distances roughly equivalent to or slightly more than the
spectrum of visual and infrared light. Although not to be held to any
particular theory, it is believed that the high absorptivity and
emissivity values obtained in the practice of the present invention are
due to this, plus the blackness of the relatively pure boron particles.
EXAMPLES 5-10
These Examples illustrate that the surfaces of the present invention have a
resistance to attack from common corrosive or oxidative agents such as
acids and solvents.
The samples were prepared following the procedure of Example 1 except that
there was no calcination posttreatment following plasma spray application
to a substrate. The substrate in these Examples was the titanium,
aluminum, vanadium alloy of Example 1. The boron form employed wa the same
crystalline boron as in Example 1.
Exposure to the corrosive agents was carried out employing conventional
etching procedures; namely, maintaining the agents at room temperature or
an elevated temperature as indicated in the following table, and then
holding the samples immersed in the solutions for a sufficient period of
time to cause etching if etching was to occur, for instance as evidenced
by the evolution of hydrogen. In all instances, there was no evidence of
etching.
TABLE 1
______________________________________
Effect on
Optical Properties
Optical
Samples
Treatment Absorptivity
Emissivity
Properties
______________________________________
Example
Exposure to a
-- -- None
5 methanol/
sulfuric acid
mixture
Example
Exposure to
0.90 0.87 None
6 an ethanol/
potassium
hydroxide
mixture
Example
Exposure to a
-- -- None
7 sulfuric acid/
chromic oxide
solution
Example
Exposure to
0.91 0.89 None
8 boiling
sulfuric acid
Example
Exposure to None
9 boiling
nitric acid
Example
Exposure to
0.89 0.86 None
10 nitric acid/
sodium
chromate
solution
______________________________________
Similar samples subjected to conventional anodizatoin also showed a
resistance or inertness to chemical reactivity under these conditions.
The low chemical reactivity characteristics of the surfaces of the present
invention permits them to be exploited in many corrosive chemical
container and flow line applications, as well as for equipment which must
be operated in a corrosive or oxidative environment.
EXAMPLE 11
The purpose of this Example is to show that the boron surfaces of the
present invention are stable to prolonged exposure at high temperatures.
In this Example, crystalline boron was plasma spray applied to the
titanium alloy substrate of Example 1, except that the substrate was first
bond coated with a nickel chromium, aluminum alloy (Metco 443) as in
Example 2. The boron powder was blended with 32% by weight glass ceramic
microspheres as in Example 2 to increase flowability. The same conditions
of application, procedures, boron powder, and spray gun as in Example 1
were used. The boron surface, following application, had an absorptivity
of about 0.91 and an emissivity of about 0.88.
The surface was subjected to calcination at 900.degree. C. for 1/2 hour.
Absorptivity actually increased slightly to about 0.92, and emissivity
remained constant at about 0.88. The surface remained visually black.
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